Surprising Stability of Larger Criegee Intermediates on Aqueous Interfaces

Jie Zhong; Manoj Kumar; Chong Q. Zhu; Joseph S. Francisco; Xiao C. Zeng

doi:10.1002/anie.201702722

Surprising Stability of Larger Criegee Intermediates on Aqueous Interfaces

Jie Zhong, Manoj Kumar, Chong Q. Zhu, Joseph S. Francisco^*, Xiao C. Zeng

^*Corresponding author for this work

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

63 Citations (Scopus)

Abstract

Criegee intermediates have implications as key intermediates in atmospheric, organic, and enzymatic reactions. However, their chemistry in aqueous environments is relatively unexplored. Herein, Born–Oppenheimer molecular dynamics (BOMD) simulations examine the dynamic behavior of syn- and anti-CH₃CHOO at the air–water interface. They show that unlike the simplest Criegee intermediate (CH₂OO), both syn- and anti-CH₃CHOO remain inert towards reaction with water. The unexpected high stability of C₂ Criegee intermediates is due to the presence of a hydrophobic methyl substituent on the Criegee carbon that lowers the proton transfer ability and inhibits the formation of a pre-reaction complex for the Criegee–water reaction. The simulation of the larger Criegee intermediates, (CH₃)₂COO, syn- and anti-CH₂C(CH₃)C(H)OO on the water droplet surface suggests that strongly hydrophobic substituents determine the reactivity of Criegee intermediates at the air–water interface.

Original language	English
Pages (from-to)	7740-7744
Journal	Angewandte Chemie - International Edition
Volume	56
Issue number	27
DOIs	https://doi.org/10.1002/anie.201702722
Publication status	Published - 26 Jun 2017
Externally published	Yes

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Publication details (e.g. title, author(s), publication statuses and dates) are captured on an “AS IS” and “AS AVAILABLE” basis at the time of record harvesting from the data source. Suggestions for further amendments or supplementary information can be sent to [email protected].

Research Keywords

ab initio dynamics simulation
air–water interface
atmospheric chemistry
Criegee intermediate

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abstract = "Criegee intermediates have implications as key intermediates in atmospheric, organic, and enzymatic reactions. However, their chemistry in aqueous environments is relatively unexplored. Herein, Born–Oppenheimer molecular dynamics (BOMD) simulations examine the dynamic behavior of syn- and anti-CH3CHOO at the air–water interface. They show that unlike the simplest Criegee intermediate (CH2OO), both syn- and anti-CH3CHOO remain inert towards reaction with water. The unexpected high stability of C2 Criegee intermediates is due to the presence of a hydrophobic methyl substituent on the Criegee carbon that lowers the proton transfer ability and inhibits the formation of a pre-reaction complex for the Criegee–water reaction. The simulation of the larger Criegee intermediates, (CH3)2COO, syn- and anti-CH2C(CH3)C(H)OO on the water droplet surface suggests that strongly hydrophobic substituents determine the reactivity of Criegee intermediates at the air–water interface.",

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AU - Zhong, Jie

AU - Kumar, Manoj

AU - Zhu, Chong Q.

AU - Francisco, Joseph S.

AU - Zeng, Xiao C.

N1 - Publication details (e.g. title, author(s), publication statuses and dates) are captured on an “AS IS” and “AS AVAILABLE” basis at the time of record harvesting from the data source. Suggestions for further amendments or supplementary information can be sent to [email protected].

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N2 - Criegee intermediates have implications as key intermediates in atmospheric, organic, and enzymatic reactions. However, their chemistry in aqueous environments is relatively unexplored. Herein, Born–Oppenheimer molecular dynamics (BOMD) simulations examine the dynamic behavior of syn- and anti-CH3CHOO at the air–water interface. They show that unlike the simplest Criegee intermediate (CH2OO), both syn- and anti-CH3CHOO remain inert towards reaction with water. The unexpected high stability of C2 Criegee intermediates is due to the presence of a hydrophobic methyl substituent on the Criegee carbon that lowers the proton transfer ability and inhibits the formation of a pre-reaction complex for the Criegee–water reaction. The simulation of the larger Criegee intermediates, (CH3)2COO, syn- and anti-CH2C(CH3)C(H)OO on the water droplet surface suggests that strongly hydrophobic substituents determine the reactivity of Criegee intermediates at the air–water interface.

AB - Criegee intermediates have implications as key intermediates in atmospheric, organic, and enzymatic reactions. However, their chemistry in aqueous environments is relatively unexplored. Herein, Born–Oppenheimer molecular dynamics (BOMD) simulations examine the dynamic behavior of syn- and anti-CH3CHOO at the air–water interface. They show that unlike the simplest Criegee intermediate (CH2OO), both syn- and anti-CH3CHOO remain inert towards reaction with water. The unexpected high stability of C2 Criegee intermediates is due to the presence of a hydrophobic methyl substituent on the Criegee carbon that lowers the proton transfer ability and inhibits the formation of a pre-reaction complex for the Criegee–water reaction. The simulation of the larger Criegee intermediates, (CH3)2COO, syn- and anti-CH2C(CH3)C(H)OO on the water droplet surface suggests that strongly hydrophobic substituents determine the reactivity of Criegee intermediates at the air–water interface.

KW - ab initio dynamics simulation

KW - air–water interface

KW - atmospheric chemistry

KW - Criegee intermediate

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Surprising Stability of Larger Criegee Intermediates on Aqueous Interfaces

Abstract

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